Match ends, Liverpool 2(5), Chelsea 2(4).
Liverpool won the Super Cup for the fourth time in their history by beating Chelsea 5-4 on penalties after a 2-2 draw in Istanbul.
Goalkeeper Adrian kept out Tammy Abraham's spot kick to secure victory for the Champions League winners.
Chelsea had taken the lead in the first half through Olivier Giroud's clinical strike but Sadio Mane scored twice to give Liverpool the lead.
Jorginho's spot-kick took the game to penalties, where Liverpool triumphed.
The win comes just two months after Jurgen Klopp won his first trophy as Liverpool boss when he led the Reds to a 2-0 win over Tottenham in the Champions League final.
Games between these two sides in Europe have historically been tight affairs, with just one of their 10 previous meetings having been won by a margin of more than one goal.
It was the same again on Wednesday night as the two teams tussled for 120 minutes in a game that did not finish until almost 1am in Istanbul.
In the end, it came down to who could keep their cool in the sweltering heat and after nine excellent penalties, Abraham placed his shot too close to Adrian to hand Liverpool their first silverware of the season.
- Football Daily podcast: Liverpool win silverware on penalties in Istanbul ... again
- Referee Frappart praised for performance
Fairytale final for Adrian
Two weeks ago Adrian was without a club, having been released by West Ham at the end of last season.
But, following Simon Mignolet's departure to Club Brugge, Klopp snapped up the 32-year-old shot-stopper to provide experienced cover for Alisson.
Adrian had barely had time to get to know his new team-mates when he was called upon earlier than expected as Liverpool's first-choice goalkeeper injured his calf in the 4-1 win against Norwich in the Premier League's season-opener last Friday.
With Alisson facing a spell on the sidelines, Adrian made his full debut against Chelsea. It was his first competitive start since January, but he showed little signs of nerves or rustiness, catching the eye in the first half when he sprung off his line to deny Mateo Kovacic from close range.
There was little he could do about Chelsea's opener, which was a clinical finish by Giroud, although he did give away the penalty deep in extra time when he took the legs of Abraham.
But that gave him the platform to produce his penalty shootout heroics, which will give him and the Liverpool fans confidence he can be an able deputy during Alisson's absence.
Two defeats, but promising signs from Chelsea
Chelsea lost 4-0 at Manchester United on Sunday and while this was another defeat for the Blues and their new manager Frank Lampard, there were plenty of positives to be taken from Wednesday night's performance.
Lampard fielded a young side at Old Trafford but turned to the older heads in his squad for this game. The added bit of experience and quality showed, particularly in a dominant first-half display.
N'Golo Kante was by far the best player on the pitch in the opening 45 minutes as he pulled the strings in midfield, while Giroud showed the clinical finishing that was absent for the Blues at the weekend.
Christian Pulisic also caught the eye on his first competitive start for Chelsea.
The 20-year-old American provided a creative spark, while his movement and vision had more than a hint of Eden Hazard about them.
One moment that caught the eye saw him run onto a through ball in the first half, cut inside before tucking a neat finish inside the near post. However, the goal was ruled out for offside following a VAR check.
If Lampard is able to get the balance of youth and experience right in his first XI, Chelsea could be an exciting team to watch this season.
Frappart impresses in historic appearance
History was made in the game as France's Stephanie Frappart became the first woman to referee a major European men's game.
The 35-year-old has officiated matches in the third division of men's football in France and refereed the Women's World Cup final in France this summer.
Frappart, who led a team largely made up of female officials which included assistant referees Manuela Nicolosi of France and Michelle O'Neill from the Republic of Ireland, was praised on social media for her performance.
She let the game flow, while VAR was not called upon in the game to overturn any of her decisions.
Man of the match
Chelsea come close again - the stats
- Only Barcelona and AC Milan (5) have won the Super Cup more times than Liverpool (4).
- Chelsea have now lost three consecutive Super Cup appearances (2012, 2013 and 2019) - only Barcelona and Sevilla (four each) have been runners-up on more occasions.
- This was the 11th match between Liverpool and Chelsea in European competition, making it the most-played European fixture between two sides from the same nation.
- With the scores level at 1-1 after 90 minutes, this was the fifth time in the past seven seasons the Super Cup has gone to extra time or penalties.
- Liverpool became the first Premier League club to be involved in two penalty shootouts in the same month since Middlesbrough in February 2007.
- Olivier Giroud has scored 12 goals in 16 appearances in European competition for Chelsea, compared with just seven goals in 49 domestic games for the Blues.
- Liverpool's Sadio Mane became the first African player to score in the Super Cup since Frederic Kanoute for Sevilla vs Barcelona in 2006.
'I've nothing but pride' - what they said
Liverpool manager Jurgen Klopp speaking to BT Sport: "It was a very difficult game for both teams. It was all about winning it and we did that in the end.
"Nobody in the stadium wanted extra time, it was a killer. I'm not sure about the penalty but who cares now.
"We started well then dropped off... we could talk about football but it's too late now. We had to fight and the boys did tonight."
Chelsea manager Frank Lampard speaking to BT Sport: "I've got nothing but pride in the team and the performance, and confidence in what that means.
"It was a tough game against a good Liverpool team that had extra time to recover after the weekend. But sometimes football comes down to little moments of luck."
Liverpool travel to Southampton in the Premier League on Saturday (15:00 BST), while Chelsea host Leicester the following day (16:00 BST)
- 4van Dijk
- 26RobertsonSubstituted forAlexander-Arnoldat 90'minutesBooked at 107mins
- 14HendersonBooked at 85mins
- 7MilnerSubstituted forWijnaldumat 64'minutes
- 10ManéSubstituted forOrigiat 103'minutes
- 15Oxlade-ChamberlainSubstituted forFirminoat 45'minutes
- 28AzpilicuetaBooked at 79mins
- 4ChristensenSubstituted forTomoriat 85'minutes
- 17KovacicSubstituted forBarkleyat 101'minutes
- 18GiroudSubstituted forAbrahamat 74'minutes
- 22PulisicSubstituted forMountat 74'minutes
- Stéphanie Frappart
- Shots on Target
Penalty Shootout ends, Liverpool 2(5), Chelsea 2(4).
Penalty saved! Tammy Abraham (Chelsea) fails to capitalise on this great opportunity, right footed shot saved in the centre of the goal.
Goal! Liverpool 2(5), Chelsea 2(4). Mohamed Salah (Liverpool) converts the penalty with a left footed shot to the bottom left corner.
Goal! Liverpool 2(4), Chelsea 2(4). Emerson (Chelsea) converts the penalty with a left footed shot to the centre of the goal.
Goal! Liverpool 2(4), Chelsea 2(3). Trent Alexander-Arnold (Liverpool) converts the penalty with a right footed shot to the bottom left corner.
Goal! Liverpool 2(3), Chelsea 2(3). Mason Mount (Chelsea) converts the penalty with a right footed shot to the top left corner.
Goal! Liverpool 2(3), Chelsea 2(2). Divock Origi (Liverpool) converts the penalty with a right footed shot to the bottom left corner.
Goal! Liverpool 2(2), Chelsea 2(2). Ross Barkley (Chelsea) converts the penalty with a right footed shot to the bottom right corner.
Goal! Liverpool 2(2), Chelsea 2(1). Fabinho (Liverpool) converts the penalty with a right footed shot to the bottom right corner.
Goal! Liverpool 2(1), Chelsea 2(1). Jorginho (Chelsea) converts the penalty with a right footed shot to the bottom left corner.
Goal! Liverpool 2(1), Chelsea 2. Roberto Firmino (Liverpool) converts the penalty with a right footed shot to the bottom left corner.
Penalty Shootout begins Liverpool 2, Chelsea 2.
Second Half Extra Time ends, Liverpool 2, Chelsea 2.
Delay over. They are ready to continue.
Delay in match because of an injury Fabinho (Liverpool).
Foul by Joel Matip (Liverpool).
Ross Barkley (Chelsea) wins a free kick in the defensive half.
Offside, Chelsea. Mason Mount tries a through ball, but Tammy Abraham is caught offside.
Attempt saved. Mason Mount (Chelsea) right footed shot from outside the box is saved in the bottom right corner. Assisted by Pedro.